Partitioning of polychlorinated biphenyls and hexachlorobenzene into human faeces

The dietary absorption of persistent lipophilic organic pollutants (PLOPs) in humans is believed to occur via partitioning of the chemical between the lumen and the wall of the digestive tract. As such, the partitioning properties of the lumen contents are a key factor governing absorption. In this study, the partitioning properties of faeces were measured for 11 polychlorinated biphenyls and hexachlorobenzene (HCB). Four volunteers participated in the study, each of them providing faeces from a normal diet and a vegetarian diet. The faeces/gas equilibrium partition coefficient K(FG) varied by over three orders of magnitude between the different compounds. A linear relationship between log K(FG) and log KOA, the octanol/air partition coefficient, was observed. The slope of the relationship was > 1, indicating that the solvent properties of faeces were less polar than those of octanol. For a given compound, KFG varied up to a factor of 2.8 between the individuals on a normal diet. The influence of the vegetarian diet on K(FG) was negligible for the two volunteers who simply deleted fish and animal products from their normal diet, but K(FG) increased on average by a factor of 2 in the two individuals who increased their consumption of less readily digestible whole grains and vegetables in their vegetarian diet. On the basis of K(FG), the fugacities in the faeces were calculated. They were found to be much lower than the fugacities in blood. It is hypothesised that this is due to a temporary decrease in the fugacity in the wall of the jejunum caused by absorption of dietary lipids that results in equilibration between the lumen contents and the wall of the digestive tract at a fugacity below that present in the blood and the rest of the body.     

Contaminant residues in seabird eggs from the Canadian Arctic. II. Spatial trends and evidence from stable isotopes for intercolony differences

Eggs of glaucous gulls (Larus hyperboreus), black-legged kittiwakes (Rissa tridactyla), thick-billed murres (Uria lomvia) and black guillemots (Cepphus grylle) were collected from several sites throughout the Canadian Arctic. Samples were analyzed for organochlorines as well as mercury and selenium. Glaucous gulls breeding at sites in the High Arctic showed higher levels of organochlorine contamination than those in the western Low Arctic. This was likely due to dietary differences among colonies as suggested by stable isotope data, although different overwintering areas may also play a role. Levels of sigmaPCB, sigmaDDT, sigmaCHLOR, sigmaCBz and dieldrin were significantly lower in thick-billed murres from Prince Leopold Island in the High Arctic compared with colonies in the eastcrn Low Arctic. This difference was likely due to the combined effects of different atmospheric deposition patterns in the High and Low Arctic and different overwintering areas since murres from Prince Leopold Island may winter farther north than murres from the other colonies sampled. Eggs from colonies at higher latitudes generally contained higher concentrations of mercury. The trophic and dietary differences/similarities suggested by stable-nitrogen and carbon isotope data in this study were useful in explaining the spatial patterns of contaminant concentrations observed among colonies of seabirds such as the glaucous gull and the black-legged kittiwake where variation in latitudinal atmospheric deposition patterns and different overwintering grounds did not appear to be confounding factors.     

EuroBionet: a pan-European biomonitoring network for urban air quality assessment

EuroBionet, the 'European Network for the Assessment of Air Quality by the Use of Bioindicator Plants', is an EU-funded cooperative project currently consisting of public authorities and scientific institutes from 12 cities in 8 countries. In 2000, the bioindicator plants tobacco (Nicotiana tabacum Bel W3), poplar (Populus nigra 'Brandaris'), spiderwort (Tradescantia sp. clone 4430), Italian rye grass (Lolium multiflorum italicum) and curly kale (Brassica oleracea acephala) were exposed to ambient air at 90 monitoring sites according to standardised methods. Visible injuries and growth parameters were assessed and the accumulation of toxic substances in leaves determined. The exposure of tobacco resulted in a gradient with low levels of ozone-induced foliar injury in N and NW Europe, and medium to high values in the southern and central regions. The results of heavy metal and sulphur analyses in rye grass samples generally showed low to very low sulphur and low to medium heavy metal concentrations in leaves. In some cities, however, local hot spots of heavy metal contamination were detected. Analyses of the PAH contents in curly kale leaves gave low to medium values, with locally elevated levels at traffic-exposed sites.     

Kinetics of chemical decolorization of the azo dye C.I. Reactive Orange 96 by sulfide

The mechanism of decolorization of azo dyes based on the extracellular chemical reduction with sulfide (H2S, HS-, S2-) was postulated for sulfate reducing environments. To design technical decolorization processes of textile wastewater treatment with sulfide produced by sulfate reducing bacteria (SRB), kinetics is of great significance. Batch experiments were made in order to investigate the kinetics of abiotic decolorization of the reactive mono-azo dye C.I. Reactive Orange 96 (RO 96) with sulfide, with varying pH. The decolorization of RO 96 by sulfide under the exclusion of O2 corresponded to first-order kinetics with respect to both dye and sulfide concentration. The decolorization of RO 96 with sulfide at neutral pH (7.1) was advantageous compared with that at pH for 4.1, 6.3, and 6.5. This is attributed to an increase in the fraction of HS- of total sulfide species at neutral pH. The rate constants k for the decolorization at 37 degrees C were obtained as 0.01 for pH = 4.1, 0.06 for pH = 6.3, 0.08 for pH = 6.5, and 0.09 for pH = 7.1 in mM(-1) min(-1). The high rate constants for sulfide at pH 6.5-7.1 support that the decolorization through SRB (i.e. by bio-sulfide) can be effective in anaerobic bacterial systems with sulfate.     

Comparative study of the suitability of three lichen species to trace-element air monitoring

To investigate the suitability of three lichen species (Cetraria islandica, Evernia prunastri, and Ramalina farinacea) as transplants to trace-element air biomonitoring, they were exposed on substratum-free supports, from July 1996 until July 1997, in three European countries with different climates (Germany, Italy, Romania), at six sites with different types of air pollutants (two in each country). After 2, 4, 6, and 12 months of exposure, some portions of thallus were collected, prepared, and measured by instrumental neutron activation analysis (INAA) at the Institute of Physics and Nuclear Engineering in Bucharest and by energy dispersive X-ray fluorescence analysis (EDXRFA) at the University of Hohenheim in Stuttgart. Fifteen environmentally relevant elements: As, Br, Ca, Co, Cr, Cu, Fe, K, Mn, Ni, Pb, S, Sb, V, and Zn were determined. The analytical results were compared statistically. To study the distribution of the trace-elements between the lichens and the lichen throughfall water inside a virtual column, the throughfall water was collected under the lichen transplants during 6 and 12 months. The dried residues were analysed by INAA at Bucharest. The accumulating capacity for all investigated species is evident. For a comparative evaluation, the initial element contents, the "accumulation factors" relative to the bulk deposition, the interspecies "calibration factors", and the "retention efficiencies", defined as ratios of the lichen enrichment to the sum of this enrichment and the content in the lichen throughfall water, were considered. These criteria attest the best suitability for Evernia prunastri, followed by Ramalina farinacea and Cetraria islandica.     

Development and calibration of epiphytic lichens as saltfall biomonitors--dry-deposition modelling

Blubber collected from beluga whales and ringed seals during subsistence hunts in the southern Baffin Island region of the Canadian Arctic were analysed for polychlorinated naphthalenes and eight planar PCB congeners (mono-ortho PCBs: 105, 114, 118 and 156; non-ortho PCBs: 77, 81, 126, 169). SigmaPCN (3-7 Cl) concentrations in blubber ranged from 35.9-383 pg/g (lipid weight; lw) in beluga and 35.4-71.3 pg/g (lw) in ringed seal. These represent the first measurements of PCNs in marine mammals in the Canadian Arctic, mammals which are an important part of the traditional diet of the indigenous population. SigmaCoplPCB concentrations were much higher, ranging from 15.5-317 ng/g (lw) in beluga whale blubber and 16.5-40.9 ng/g (lw) in ringed seal blubber. PCNs and coplanar PCBs both exhibit dioxin-like toxicity. Although average sigmaPCN concentrations were less than 1% of sigmaCoplPCBs, PCNs contribute up to 11% of TEQ relative to the coplanar PCBs based on TEFs determined by H4IIE enzyme assays.     

Natural attenuation of chlorinated solvents at Area 6, Dover Air Force Base: groundwater biogeochemistry

Monitored natural attenuation (MNA) has recently emerged as a viable groundwater remediation technology in the United States. Area 6 at Dover Air Force Base (Dover, DE) was chosen as a test site to examine the potential for MNA of tetrachloroethene (PCE) and trichloroethene (TCE) in groundwater and aquifer sediments. A "lines of evidence" approach was used to document the occurrence of natural attenuation. Chlorinated hydrocarbon and biogeochemical data were used to develop a site-specific conceptual model where both anaerobic and aerobic biological processes are responsible for the destruction of PCE, TCE, and daughter metabolites. An examination of groundwater biogeochemical data showed a region of depleted dissolved oxygen with elevated dissolved methane and hydrogen concentrations. Reductive dechlorination likely dominated in the anaerobic portion of the aquifer where PCE and TCE levels were observed to decrease with a simultaneous increase in cis-1,2-dichloroethene (cis-DCE), vinyl chloride (VC), ethene, and dissolved chloride. Near the anaerobic/ aerobic interface, concentrations of cis-DCE and VC decreased to below detection limits, presumably due to aerobic biotransformation processes. Therefore, the contaminant and daughter product plumes present at the site appear to have been naturally atteuated by a combination of active anaerobic and aerobic biotransformation processes.     

Cobalt-based alumina pillared zirconium phosphate catalysts for the selective catalytic reduction of NO by propane

A series of cobalt containing alumina pillared zirconium phosphate materials have been prepared by ion exchange or by impregnation, and fully characterised. The catalytic behaviour of these materials in the selective catalytic reduction of NO by propane, in excess of oxygen, at temperatures ranging between 350 and 550 degrees C, has been also evaluated. A maximum NO conversion close to 14% is obtained on Co-impregnated catalysts heated at 600 degrees C. The NO reduction seems to be related to the presence of Co3+, thus the calcination temperature of samples influences the resulting activity much more than the cobalt content.     

Sequential anaerobic-aerobic treatment of an aquifer contaminated by halogenated organics: field results

In situ, sequential, anaerobic to aerobic treatment of groundwater removed perchloroethene (PCE, 1.1 microM) and benzene (0.8 microM) from a contaminated aquifer. Neither aerobic nor anaerobic treatment alone successfully degraded both the chlorinated and non-chlorinated organic contaminants in the aquifer. After the sequential treatment, PCE, trichloroethene (TCE), vinyl chloride (VC), chloroethane (CA), and benzene were not detectable in groundwater. Desorption of residual aquifer contaminants was tested by halting the groundwater recirculation and analyzing the groundwater after 3 and 7 weeks. No desorption of the chlorinated contaminants or daughter products was observed in the treated portion of the aquifer. Sequential anaerobic to aerobic treatment was successful in remediating the groundwater at this test site and may have broad applications at other contaminated sites. Over the 4-year course of the project, the predominant microbial environment of the test site varied from aerobic to sulfate-reducing, to methanogenic, and back to aerobic conditions. Metabolically active microbial populations developed under all conditions, demonstrating the diversity and robustness of natural microbial flora in the aquifer.     

Performance assessment of NAPL remediation in heterogeneous alluvium

Over the last few years, more than 40 partitioning interwell tracer tests (PITTs) have been conducted at many different sites to measure nonaqueous phase liquid (NAPL) saturations in the subsurface. While the main goal of these PITTs was to estimate the NAPL volume in the subsurface, some were specifically conducted to assess the performance of remedial actions involving NAPL removal. In this paper, we present a quantitative approach to assess the performance of remedial actions to recover NAPL that can be used to assess any NAPL removal technology. It combines the use of PITTs (to estimate the NAPL volume in the swept pore volume between injection and extraction wells of a test area) with the use of several cores to determine the vertical NAPL distribution in the subsurface. We illustrate the effectiveness of such an approach by assessing the performance of a surfactant/foam flood conducted at Hill Air Force Base, UT, to remove a TCE-rich NAPL from alluvium with permeability contrasts as high as one order of magnitude. In addition, we compare the NAPL volumes determined by the PITTs with volumes estimated through geostatistical interpolation of aquifer sediment core data collected with a vertical frequency of 5-10 cm and a lateral borehole spacing of 0.15 m. We demonstrate the use of several innovations including the explicit estimation of not only the errors associated with NAPL volumes and saturations derived from PITTs but also the heterogeneity of the aquifer sediments based upon permeability estimates. Most importantly, we demonstrate the reliability of the